EP0349363B1 - Article and process for absorbing polluting products - Google Patents
Article and process for absorbing polluting products Download PDFInfo
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- EP0349363B1 EP0349363B1 EP89401625A EP89401625A EP0349363B1 EP 0349363 B1 EP0349363 B1 EP 0349363B1 EP 89401625 A EP89401625 A EP 89401625A EP 89401625 A EP89401625 A EP 89401625A EP 0349363 B1 EP0349363 B1 EP 0349363B1
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- Prior art keywords
- polymer
- cover
- agent
- article according
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/918—Miscellaneous specific techniques
- Y10S210/922—Oil spill cleanup, e.g. bacterial
- Y10S210/924—Oil spill cleanup, e.g. bacterial using physical agent, e.g. sponge, mop
Definitions
- the present invention relates to the field of depollution of liquid or solid surfaces.
- Patent FR-A-2,288,709 also describes a process for removing and recovering petroleum products, in particular heavy hydrocarbons, spread on a liquid or solid surface by bringing said petroleum product into contact with a finely divided polymer capable of producing with the petroleum product a film having sufficient strength to be able to be towed, then removal of said film by mechanical means.
- a preferred polymer for carrying out this process is a polymer of bicyclo (2.2.1) heptene-2 or of its methyl derivative, these polymers forming with petroleum hydrocarbons a coherent film which may contain up to 10 parts by weight of petroleum products for a part of polymer.
- the contacting of the polymer with the petroleum product is carried out, according to this known process, by simple dusting of the polymer on the surface of said product.
- the absorbency of the bicyclo (2.2.1.) Heptene-2 polymer can reach 15 and even 40 parts by weight of hydrocarbon per 1 part of polymer, while leading to dry absorbates, free from any subsequent exudation of the hydrocarbon even under a pressure of 3 to 70 bars.
- absorbents no longer have sufficient cohesion to be able to be removed in the form of towable film. Rather, they are semi-agglomerated masses in the form of gelatin which are difficult to collect and / or to evacuate.
- the Applicant has found that the problems mentioned above, linked to the spreading of powdered polymer in windy weather, to the structure of certain absorbents, to the kinetics of absorption and / or to the aging of the polymer can be judiciously overcome. , thanks to the present invention, by plasticizing the polymer and enclosing the plasticized polymer powder in a fine mesh textile cover, the ends of which are closed after introduction of the polymer.
- a first object of the present invention therefore consists of a depollution article comprising a powdered polymer of bicyclo (2.2.1) heptene-2 or of its methyl derivative, characterized in that it comprises at least one mesh textile cover. fine at least partially filled with said polymer, the latter being agglomerated beforehand by an agent imparting to it a certain plasticization.
- the cover forming part of the depollution article according to the invention can be made of any textile material, woven or nonwoven, chosen in particular from synthetic materials such as nylon, polyester, polypropylene, viscose or mixtures thereof or even from natural materials such as cotton. It can also be made of an extensible textile material. Said cover can be of any shape such as for example a cushion, sausage shape or any other. It can have various dimensions adapted to the intended application and chosen in particular between 3 centimeters and 10 meters approximately, without these figures being of a limiting nature. In order to prevent the polymer contained in the cover from escaping, it is obviously important that the sides and / or the ends of the cover are closed by any means of closure, for example that they are sewn, knotted or encircled after filling of said polymer.
- the cover usable according to the present invention may also comprise, preferably fixed to at least one of its ends, at least one gripping means such as a fastener or a knot allowing it to be pulled or towed by mechanical means usual.
- the textile cover forming part of the depollution article according to the invention has a fine mesh allowing the liquid polluting product (petroleum, oil, hydrocarbon light or other) to enter the cover and come into contact with the agglomerated polymer.
- the mesh of the textile cover must have a dimension less than the dimension of almost all (preferably at least 95%) of the particles of the agglomerated polymer.
- the fine mesh textile cover must be at least partially filled with agglomerated polymer of bicyclo (2.2.1) heptene-2 or its methylated derivative.
- partial filling is meant that the cover does not necessarily have to be filled with the maximum quantity of polymer that its geometric shape could theoretically allow, this in order to provide a residual volume available for the polluting products to be absorbed by the agglomerated polymer and in order to '' avoid the risk of breaking the closure system of the cover, such as sewing or other.
- the agglomerated polymer will fill from 20% to 80% approximately of the theoretical volume of the cover.
- the polymer contained in the cover is in the form of a coarse powder with an apparent density of between 0.15 and 0.50 approximately and a particle size of between 0.5 and 20 mm approximately.
- the powdered polymers of bicyclo (2.2.1) heptene-2 or of its methylated derivative are well known and can be added, during or after their manufacture, fillers playing a role called anti-caking agents, such as silica, talc, calcium, sodium or zinc sterates and / or compatibilizers.
- said polymer must necessarily be agglomerated by means of an agent imparting to it a certain plasticization, such as liquid hydrocarbons and petroleum, paraffinic, aromatic or naphthenic oils, phthalates, adipates, sebacates, alkylbenzenes, etc.
- the proportion of the plasticizing agent relative to the polymer can be between 0.5 and 50% by weight, and preferably between 5 and 35% by weight.
- the material capable of absorbing liquid pollutants and filling the cover may consist of a mixture of agglomerated polymer of bicyclo (2.2.1) heptene-2 and at least one other agent absorbing pollutants, the proportion of this other absorbent agent in the mixture being at most equal to approximately 97% by weight, preferably at most equal to approximately 40% by weight.
- pollutant absorbing agents which can be used in the context of this variant of the present invention, there may be mentioned in particular organic agents such as polymers based on olefin (proplyene, ethylene, etc.) or styrene, fibrous or in powder, regenerated or not, compact or expanded, plant agents such as peanut husk or cereal waste and mineral agents such as clay, chalk, silica, silicates, alumina or fly ash.
- organic agents such as polymers based on olefin (proplyene, ethylene, etc.) or styrene, fibrous or in powder, regenerated or not, compact or expanded, plant agents such as peanut husk or cereal waste and mineral agents such as clay, chalk, silica, silicates, alumina or fly ash.
- a second object of the present invention consists of a method for absorbing a liquid polluting product, characterized in that there is at the surface of said liquid at least one fine mesh textile cover filled at least partially with a powdered polymer of bicyclo (2.2.1) heptene-2 or its methyl derivative, said polymer being previously agglomerated by an agent imparting to it a certain plasticization.
- the method according to the invention therefore consists in using the depollution article described above to absorb a liquid pollutant. It is particularly applicable on a liquid surface such as that of a sea, a lake or a watercourse when pollutants have been accidentally spilled there. It is also applicable on a solid surface, such as a floor on which a machine (for example lathe or milling machine) lets oil leak. This process is more particularly applicable to the case where the polluting product is a petroleum product, in particular a hydrocarbon or a lubricant or hydraulic fluid.
- the number of covers to be used must be adapted according to the exact nature of the petroleum hydrocarbons spilled on the polluted surface.
- the absorption capacity of the agglomerated polymer of bicyclo (2.2.1) heptene-2 varies greatly from one fraction of hydrocarbons to another: while it generally reaches around 1 to 10 parts by weight of hydrocarbon for 1 part of polymer in the case of heavy hydrocarbons, as mentioned by the patent FR-A-2,288,709 cited above, it has been surprisingly discovered that it can reach up to 40 parts by weight of hydrocarbons for 1 part by weight of agglomerated polymer in the case of transformer oils and lighter hydrocarbons such as household fuel, benzene, toluene and xylene.
- the number of textile covers placed on the polluted surface, when the polluting product is an petroleum product is therefore chosen in such a way that the quantity of agglomerated polymer contained in all of the covers is between 1/40 and 1 times the quantity of polluting product to be absorbed.
- the time necessary for the absorption of polluting products by the agglomerated polymer contained in the textile cover depends on the one hand on the chemical nature of said polluting products, on the other hand on their mode of distribution, compact or dispersed, on the polluted surface .
- this time depends on whether they are heavy or light hydrocarbons. In the latter case, this time is generally between 5 seconds and 1 hour approximately, at room temperature.
- the time required for the absorption of polluting products by the agglomerated polymer is advantageously less than the time required by the use of a non-agglomerated powder polymer.
- the cover and its contents can be easily removed, in particular by means of the gripping means indicated above, without risk of exudation and / or flow, for example to a point of authorized landfill or to a place of incineration.
- a polybicyclo (2.2.1) heptene-2 sold by the applicant under the trademark NORSOREX is sieved through a sieve of size 0.1 mm.
- the rejection of a sieve, with a particle size between 0.1 and 0.8 mm, is added with 1% of stearic acid.
- 500 g of this mixture, with a bulk density of 0.40, are introduced into a polyester textile cover 1 meter long and 55 mm in diameter, the two ends of which are closed by means of metal rings.
- the polymer absorbed the oil after 10 minutes of mixing and is then in the form of particles of 0.5 to 2 mm and has a bulk density of 0.30.
- Example 2 The procedure of Example 2 is reproduced with the following exception: the quantity of naphthenic petroleum oil used is 30 parts by weight instead of 15 parts.
- the mixture is in the form of particles from 0.5 to 10 mm and has a bulk density of 0.25.
- the time t2 observed as a function of the time t1 is indicated in Table III below. TABLE III t1 8 180 360 t2 15 17 20
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- Environmental & Geological Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Medicinal Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Public Health (AREA)
- Materials Engineering (AREA)
- Removal Of Floating Material (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
La présente invention se rapporte au domaine de la dépollution de surfaces liquides ou solides.The present invention relates to the field of depollution of liquid or solid surfaces.
On connaît déjà, notamment par les brevets US-A-4.366.067, FR-A-2.090.452 et EP-A-0.027.359, des articles destinés à éliminer du pétrole et/ou des huiles présents à la surface d'un liquide, comprenant un emballage ou sac en tissu ou autre matériau rempli de plumes d'oiseaux, de perlite expansée ou encore de mousse de polyisocyanurate à cellules fermées. L'absorption de pétrole et/ou d'huiles par ces produits s'avère toutefois nettement insuffisante.Are already known, in particular from patents US-A-4,366,067, FR-A-2,090,452 and EP-A-0,027,359, articles intended for removing petroleum and / or oils present on the surface of a liquid, comprising a fabric or other packaging or bag filled with bird feathers, expanded perlite or even closed cell polyisocyanurate foam. However, the absorption of petroleum and / or oils by these products is clearly insufficient.
Le brevet FR-A-2.288.709 décrit par ailleurs un procédé d'enlèvement et de récupération de produits pétroliers, notamment d'hydrocarbures lourds, répandus sur une surface liquide ou solide par mise en contact, avec ledit produit pétrolier, d'un polymère finement divisé capable de produire avec le produit pétrolier une pellicule possédant une résistance suffisante pour pouvoir être tractée,puis enlèvement de ladite pellicule par des moyens mécaniques. Un polymère préféré pour la mise en oeuvre de ce procédé est un polymère du bicyclo(2.2.1)heptène-2 ou de son dérivé méthylé, ces polymères formant avec les hydrocarbures pétroliers une pellicule cohérente pouvant contenir jusqu'à 10 parties en poids de produits pétroliers pour une partie de polymère. La mise en contact du polymère avec le produit pétrolier s'effectue, selon ce procédé connu, par simple saupoudrage du polymère à la surface dudit produit. Il a toutefois été constaté que l'emploi de ces polymères par saupoudrage sur les nappes de produits pétroliers présente l'inconvénient, dans les conditions météorologiques difficiles qui prévalent souvent durant les opérations de dépollution d'urgence et notamment par temps de vent, de conduire à l'entraînement d'une partie importante de la poudre de polymère en dehors de l'aire polluée visée et, par conséquent, de diminuer l'efficacité de l'opération.Patent FR-A-2,288,709 also describes a process for removing and recovering petroleum products, in particular heavy hydrocarbons, spread on a liquid or solid surface by bringing said petroleum product into contact with a finely divided polymer capable of producing with the petroleum product a film having sufficient strength to be able to be towed, then removal of said film by mechanical means. A preferred polymer for carrying out this process is a polymer of bicyclo (2.2.1) heptene-2 or of its methyl derivative, these polymers forming with petroleum hydrocarbons a coherent film which may contain up to 10 parts by weight of petroleum products for a part of polymer. The contacting of the polymer with the petroleum product is carried out, according to this known process, by simple dusting of the polymer on the surface of said product. However, it has been observed that the use of these polymers by dusting on the slicks of petroleum products has the drawback, under the difficult meteorological conditions which often prevail during emergency depollution operations and especially in windy weather, of driving entraining a large part of the polymer powder outside the targeted polluted area and, consequently, reducing the efficiency of the operation.
Par ailleurs dans certains cas, notamment celui des huiles de transformateurs et celui d'hydrocarbures légers tels que fuel domestique, solvants, benzène, toluène et xylènes, le pouvoir absorbant du polymère de bicyclo (2.2.1.)heptène-2 peut atteindre 15 et même 40 parties en poids d'hydrocarbure pour 1 partie de polymère, tout en conduisant à des absorbats secs, dépourvus de toute exsudation ultérieure de l'hydrocarbure même sous une pression de 3 à 70 bars. De tels absorbats n'ont cependant plus une cohésion suffisante pour pouvoir être enlevés sous forme de pellicule tractable. Il s'agit plutôt de masses semi-agglomérées se présentant sous une forme de gélatine difficile à ramasser et/ou à évacuer.Furthermore, in certain cases, in particular that of transformer oils and that of light hydrocarbons such as household fuel, solvents, benzene, toluene and xylenes, the absorbency of the bicyclo (2.2.1.) Heptene-2 polymer can reach 15 and even 40 parts by weight of hydrocarbon per 1 part of polymer, while leading to dry absorbates, free from any subsequent exudation of the hydrocarbon even under a pressure of 3 to 70 bars. However, such absorbents no longer have sufficient cohesion to be able to be removed in the form of towable film. Rather, they are semi-agglomerated masses in the form of gelatin which are difficult to collect and / or to evacuate.
Enfin la mise en oeuvre du procédé selon le brevet FR-A-2.288.709 se heurte d'une part à l'insuffisance de la cinétique d'absorption des hydrocarbures et/ou des huiles de transformateurs par le polymère de bicyclo(2.2.1.)heptène-2, d'autre part au vieillissement de ce polymère à l'issue d'un stockage prolongé.Finally, the implementation of the process according to patent FR-A-2,288,709 comes up against, on the one hand, the insufficient kinetics of absorption of hydrocarbons and / or transformer oils by the bicyclo polymer (2.2. 1.) heptene-2, on the other hand upon aging of this polymer after prolonged storage.
La demanderesse a trouvé que les problèmes évoqués ci-dessus, liés à l'épandage de polymère en poudre par temps de vent, à la structure de certains absorbats, à la cinétique d'absorption et/ou au vieillissement du polymère peuvent être judicieusement surmontés, grâce à la présente invention, en plastifiant le polymère et en enfermant la poudre de polymère plastifié dans une housse en textile à maille fine dont les extrémités sont fermées après introduction du polymère.The Applicant has found that the problems mentioned above, linked to the spreading of powdered polymer in windy weather, to the structure of certain absorbents, to the kinetics of absorption and / or to the aging of the polymer can be judiciously overcome. , thanks to the present invention, by plasticizing the polymer and enclosing the plasticized polymer powder in a fine mesh textile cover, the ends of which are closed after introduction of the polymer.
Un premier objet de la présente invention consiste donc en un article de dépollution comprenant un polymère en poudre de bicyclo(2.2.1) heptène-2 ou de son dérivé méthylé, caractérisé en ce qu'il comprend au moins une housse en textile à maille fine remplie au moins partiellement dudit polymère, celui-ci étant préalablement aggloméré par un agent lui impartissant une certaine plastification.A first object of the present invention therefore consists of a depollution article comprising a powdered polymer of bicyclo (2.2.1) heptene-2 or of its methyl derivative, characterized in that it comprises at least one mesh textile cover. fine at least partially filled with said polymer, the latter being agglomerated beforehand by an agent imparting to it a certain plasticization.
La housse faisant partie de l'article de dépollution selon l'invention peut être réalisée en un matériau textile quelconque, tissé ou non-tissé, choisi notamment parmi les matériaux synthétiques tels que nylon, polyester, polypropylène, viscose ou leurs mélanges ou encore parmi les matériaux naturels tels que le coton. Elle peut également être réalisée en un matériau textile extensible. Ladite housse peut être de forme quelconque telle que par exemple une forme de coussin, de boudin ou toute autre. Elle peut avoir des dimensions diverses adaptées, à l'application visée et choisies notamment entre 3 centimètres et 10 mètres environ, sans que ces valeurs chiffrées présentent un caractère limitatif. Afin d'éviter que le polymère contenu dans la housse puisse s'échapper, il est évidemment important que les côtés et/ou les extrémités de la housse soient obturés par un moyen de fermeture quelconque, par exemple qu'ils soient cousus, noués ou cerclés après remplissage dudit polymère.The cover forming part of the depollution article according to the invention can be made of any textile material, woven or nonwoven, chosen in particular from synthetic materials such as nylon, polyester, polypropylene, viscose or mixtures thereof or even from natural materials such as cotton. It can also be made of an extensible textile material. Said cover can be of any shape such as for example a cushion, sausage shape or any other. It can have various dimensions adapted to the intended application and chosen in particular between 3 centimeters and 10 meters approximately, without these figures being of a limiting nature. In order to prevent the polymer contained in the cover from escaping, it is obviously important that the sides and / or the ends of the cover are closed by any means of closure, for example that they are sewn, knotted or encircled after filling of said polymer.
La housse utilisable selon la présente invention pourra également comporter, fixé de préférence à au moins l'une de ses extrémités, au moins un moyen de préhension tel qu'une attache ou un noeud permettant de la tirer ou de la tracter par des moyens mécaniques habituels.The cover usable according to the present invention may also comprise, preferably fixed to at least one of its ends, at least one gripping means such as a fastener or a knot allowing it to be pulled or towed by mechanical means usual.
Par ailleurs il est également important que la housse en textile faisant partie de l'article de dépollution selon l'invention possède une maille fine permettant au produit polluant liquide (pétrole, huile, hydrocarbure léger ou autre) d'entrer dans la housse et de venir au contact du polymère aggloméré. On entend par là que la maille de la housse textile doit avoir une dimension inférieure à la dimension de la quasi-totalité (de préférence au moins 95 %) des particules du polymère aggloméré.Furthermore, it is also important that the textile cover forming part of the depollution article according to the invention has a fine mesh allowing the liquid polluting product (petroleum, oil, hydrocarbon light or other) to enter the cover and come into contact with the agglomerated polymer. By this is meant that the mesh of the textile cover must have a dimension less than the dimension of almost all (preferably at least 95%) of the particles of the agglomerated polymer.
Selon la présente invention, la housse en textile à maille fine doit être remplie au moins partiellement de polymère aggloméré de bicyclo(2.2.1)heptène-2 ou de son dérivé méthylé. Par remplissage partiel on entend que la housse ne doit pas nécessairement être remplie de la quantité maximale de polymère que sa forme géométrique pourrait théoriquement autoriser, ceci afin de ménager un volume résiduel disponible pour les produits polluants devant être absorbés par le polymère aggloméré et afin d'éviter les risques de rupture du système de fermeture de la housse, tel que couture ou autre. De préférence le polymère aggloméré remplira de 20% à 80% environ du volume théorique de la housse. Le polymère contenu dans la housse se présente sous forme d'une poudre grossière de densité apparente comprise entre 0,15 et 0,50 environ et de dimension de particules comprise entre 0,5 et 20 mm environ. Les polymères en poudre du bicyclo(2.2.1)heptène-2 ou de son dérivé méthylé sont bien connus et peuvent être additionnés, au cours de ou après leut fabrication, de charges jouant un rôle dit d'agents anti-mottants, tel que silice, talc, stérates de calcium, de sodium ou de zinc et/ou d'agents compatibilisants. Selon la présente invention, ledit polymère doit nécessairement être aggloméré au moyen d'un agent lui impartissant une certaine plastification tel que des hydrocarbures liquides et huiles pétrolière, paraffiniques, aromatiques ou naphténiques, des phtalates, adipates, sebaçates, des alkylbenzènes, etc. La proportion de l'agent de plastification par rapport au polymère peut être comprise entre 0,5 et 50 % en poids, et de préférence entre 5 et 35% en poids.According to the present invention, the fine mesh textile cover must be at least partially filled with agglomerated polymer of bicyclo (2.2.1) heptene-2 or its methylated derivative. By partial filling is meant that the cover does not necessarily have to be filled with the maximum quantity of polymer that its geometric shape could theoretically allow, this in order to provide a residual volume available for the polluting products to be absorbed by the agglomerated polymer and in order to '' avoid the risk of breaking the closure system of the cover, such as sewing or other. Preferably, the agglomerated polymer will fill from 20% to 80% approximately of the theoretical volume of the cover. The polymer contained in the cover is in the form of a coarse powder with an apparent density of between 0.15 and 0.50 approximately and a particle size of between 0.5 and 20 mm approximately. The powdered polymers of bicyclo (2.2.1) heptene-2 or of its methylated derivative are well known and can be added, during or after their manufacture, fillers playing a role called anti-caking agents, such as silica, talc, calcium, sodium or zinc sterates and / or compatibilizers. According to the present invention, said polymer must necessarily be agglomerated by means of an agent imparting to it a certain plasticization, such as liquid hydrocarbons and petroleum, paraffinic, aromatic or naphthenic oils, phthalates, adipates, sebacates, alkylbenzenes, etc. The proportion of the plasticizing agent relative to the polymer can be between 0.5 and 50% by weight, and preferably between 5 and 35% by weight.
Par remplissage partiel de la housse on entend, selon une variante de réalisation de la présente invention, que la matière capable d'absorber des polluants liquides et remplissant la housse peut être constituée d'un mélange de polymère aggloméré de bicyclo(2.2.1)heptène-2 et d'au moins un autre agent absorbant de produits polluants, la proportion de cet autre agent absorbant dans le mélange étant au plus égale à 97% en poids environ, de préférence au plus égale à 40% en poids environ. Parmi les autres agents absorbants de produits polluants utilisables dans le cadre de cette variante de la présente invention, on peut citer notamment des agents organiques tels que des polymères à base d'oléfine (proplyène, éthylène, etc) ou de styrène, fibreux ou en poudre, régènérés ou non, compacts ou expansés, des agents végétaux tels que des déchets de cosse d'arachide ou de céréales et des agents minéraux tels que argile, craie, silice, silicates, alumine ou cendres volantes.By partial filling of the cover is meant, according to an alternative embodiment of the present invention, that the material capable of absorbing liquid pollutants and filling the cover may consist of a mixture of agglomerated polymer of bicyclo (2.2.1) heptene-2 and at least one other agent absorbing pollutants, the proportion of this other absorbent agent in the mixture being at most equal to approximately 97% by weight, preferably at most equal to approximately 40% by weight. Among the other pollutant absorbing agents which can be used in the context of this variant of the present invention, there may be mentioned in particular organic agents such as polymers based on olefin (proplyene, ethylene, etc.) or styrene, fibrous or in powder, regenerated or not, compact or expanded, plant agents such as peanut husk or cereal waste and mineral agents such as clay, chalk, silica, silicates, alumina or fly ash.
Un second objet de la présente invention consiste en un procédé pour absorber un produit polluant liquide, caractérisé en ce qu'on dispose à la surface dudit liquide au moins une housse en textile à maille fine remplie au moins partiellement d'un polymère en poudre de bicyclo(2.2.1)heptène-2 ou de son dérivé méthylé, ledit polymère étant préalablement aggloméré par un agent lui impartissant une certaine plastification.A second object of the present invention consists of a method for absorbing a liquid polluting product, characterized in that there is at the surface of said liquid at least one fine mesh textile cover filled at least partially with a powdered polymer of bicyclo (2.2.1) heptene-2 or its methyl derivative, said polymer being previously agglomerated by an agent imparting to it a certain plasticization.
Le procédé selon l'invention consiste donc à utiliser l'article de dépollution décrit précédemment pour absorber un polluant liquide. Il est notamment applicable sur une surface liquide telle que celle d'une mer, d'un lac ou d'un cours d'eau lorsque des produits polluants y ont été malencontreusement déversés. Il est également applicable sur une surface solide, telle qu'un sol sur lequel une machine (par exemple tour ou fraiseuse) laisse fuir de l'huile. Ce procédé est plus particulièrement applicable au cas où le produit polluant est un produit pétrolier, notamment un hydrocarbure ou un lubrifiant ou fluide hydraulique. Pour la mise en oeuvre du procédé selon l'invention, le nombre de housses à utiliser devra être adapté en fonction de la nature exacte des hydrocarbures pétroliers répandus sur la surface polluée. En effet la capacité d'absorption du polymère aggloméré de bicyclo(2.2.1)heptène-2 varie fortement d'une fraction d'hydrocarbures à une autre: alors qu'elle atteint généralement de l'ordre de 1 à 10 parties en poids d'hydrocarbure pour 1 partie de polymère dans le cas des hydrocarbures lourds, comme mentionné par le brevet FR-A-2.288.709 cité précédemment, on a découvert de manière surprenante qu'elle peut atteindre jusqu'à 40 parties en poids d'hydrocarbures pour 1 partie en poids de polymère aggloméré dans le cas d'huiles de transformateurs et d'hydrocarbures plus légers tels que fuel domestique, benzène, toluène et xylène. Selon un mode de réalisation du procédé selon l'invention, le nombre de housses textiles disposées sur la surface polluée, lorsque le produit polluant est un produit pétrolier, est donc choisi de telle manière que la quantité de polymère aggloméré contenu dans l'ensemble des housses soit compris entre 1/40 et 1 fois la quantité de produit polluant à absorber.The method according to the invention therefore consists in using the depollution article described above to absorb a liquid pollutant. It is particularly applicable on a liquid surface such as that of a sea, a lake or a watercourse when pollutants have been accidentally spilled there. It is also applicable on a solid surface, such as a floor on which a machine (for example lathe or milling machine) lets oil leak. This process is more particularly applicable to the case where the polluting product is a petroleum product, in particular a hydrocarbon or a lubricant or hydraulic fluid. For the implementation of the method according to the invention, the number of covers to be used must be adapted according to the exact nature of the petroleum hydrocarbons spilled on the polluted surface. Indeed, the absorption capacity of the agglomerated polymer of bicyclo (2.2.1) heptene-2 varies greatly from one fraction of hydrocarbons to another: while it generally reaches around 1 to 10 parts by weight of hydrocarbon for 1 part of polymer in the case of heavy hydrocarbons, as mentioned by the patent FR-A-2,288,709 cited above, it has been surprisingly discovered that it can reach up to 40 parts by weight of hydrocarbons for 1 part by weight of agglomerated polymer in the case of transformer oils and lighter hydrocarbons such as household fuel, benzene, toluene and xylene. According to one embodiment of the method according to the invention, the number of textile covers placed on the polluted surface, when the polluting product is an petroleum product, is therefore chosen in such a way that the quantity of agglomerated polymer contained in all of the covers is between 1/40 and 1 times the quantity of polluting product to be absorbed.
Le temps nécessaire à l'absorption des produits polluants par le polymère aggloméré contenu dans la housse textile dépend d'une part de la nature chimique desdits produits polluants, d'autre part de leur mode de répartition, compacte ou dispersée, sur la surface polluée. En ce qui concerne ces produits pétroliers, ce temps dépend du fait de savoir s'il s'agit d'hydrocarbures lourds ou légers. Dans ce dernier cas, ce temps est généralement compris entre 5 secondes et 1 heure environ, à température ambiante. Dans tous les cas, le temps nécessaire à l'absoption des produits polluants par le polymère aggloméré est avantageusement inférieur au temps requis par l'emploi d'un polymère en poudre non aggloméré. Une fois l'essentiel des produits polluants absorbé par le polymère, la housse et son contenu peuvent être aisément évacués, notamment grâce au moyen de préhension indiqué précédemment, sans risques d'exsudation et/ou d'écoulement, par exemple vers un point de décharge autorisée ou encore vers un lieu d'incinération.The time necessary for the absorption of polluting products by the agglomerated polymer contained in the textile cover depends on the one hand on the chemical nature of said polluting products, on the other hand on their mode of distribution, compact or dispersed, on the polluted surface . For these petroleum products, this time depends on whether they are heavy or light hydrocarbons. In the latter case, this time is generally between 5 seconds and 1 hour approximately, at room temperature. In all cases, the time required for the absorption of polluting products by the agglomerated polymer is advantageously less than the time required by the use of a non-agglomerated powder polymer. Once most of the pollutants have been absorbed by the polymer, the cover and its contents can be easily removed, in particular by means of the gripping means indicated above, without risk of exudation and / or flow, for example to a point of authorized landfill or to a place of incineration.
Les exemples ci-après sont donnés à titre illustratif et non limitatif de la présente invention.The examples below are given by way of illustration and without limitation of the present invention.
On tamise un polybicyclo(2.2.1) heptène-2 commercialisé par la demanderesse sous la marque NORSOREX sur un tamis de taille 0,1 mm. Le refus de tamis, de granulométrie comprise entre 0,1 et 0,8 mm, est additionné de 1% d'acide stéarique. On introduit 500 g de ce mélange, de densité en vrac de 0,40, dans une housse en textile polyester de 1 mètre de long et 55 mm de diamètre, et dont les deux extrémités sont obturées au moyen de bagues métalliques.A polybicyclo (2.2.1) heptene-2 sold by the applicant under the trademark NORSOREX is sieved through a sieve of size 0.1 mm. The rejection of a sieve, with a particle size between 0.1 and 0.8 mm, is added with 1% of stearic acid. 500 g of this mixture, with a bulk density of 0.40, are introduced into a polyester textile cover 1 meter long and 55 mm in diameter, the two ends of which are closed by means of metal rings.
A l'issue d'un temps t₁ (exprimé en jours) après sa confection, on dispose cette housse dans un bac de rétention de 120 cm de long et 30 cm de large, contenant 1,5 kg de fuel-oil domestique. Le fuel-oil est progressivement absorbé par le contenu de la housse. A l'issue d'un temps t₂ (exprimé en minutes) après la mise en contact, tout le fuel-oil a migré et se trouve emprisonné par la housse. Le fond du bac de rétention est quasi-totalement sec. La housse et son contenu peuvent être évacués sans risque d'exsudation ou d'écoulement. La même observation peut être faite lorsque la même quantité de fuel-oil domestique est répandue à la surface d'un bac contenant de l'eau. Le temps t₂ observé en fonction du temps t₁ est indiqué dans le tableau I ci-après.
On réalise, dans un mélangeur à poudre dit mélangeur planétaire, à température ambiante, un mélange de 100 parties en poids de polybicyclo(2.2.1) heptène-2 commercialisé sous la marque NORSOREX, contenant 1 % d'acide stéarique, avec 15 parties en poids d'huile pétrolière naphténique commercialisée par la société NYNAS sous la marque NYTEX 00.In a powder mixer known as a planetary mixer, room temperature, a mixture of 100 parts by weight of polybicyclo (2.2.1) heptene-2 sold under the brand NORSOREX, containing 1% of stearic acid, with 15 parts by weight of naphthenic petroleum oil marketed by the company NYNAS under the brand NYTEX 00.
Le polymère a absorbé l'huile au bout de 10 minutes de mélangeage et se présente alors sous forme de particules de 0,5 à 2 mm et possède une densité en vrac de 0,30.The polymer absorbed the oil after 10 minutes of mixing and is then in the form of particles of 0.5 to 2 mm and has a bulk density of 0.30.
On introduit 575 g de ce mélange dans une housse identique à celle de l'exemple 1. Après obturation ds extrémités de la housse, celle-ci est soumise au test d'absorption de l'exemple 1. Le temps t₂ observé en fonction du temps t₁ est indiqué au tableau II ci-après.
On reproduit la procédure de l'exemple 2 à l'exception suivante près : la quantité d'huile pétrolière naphténique utilisée est de 30 parties en poids au lieu de 15 parties.The procedure of Example 2 is reproduced with the following exception: the quantity of naphthenic petroleum oil used is 30 parts by weight instead of 15 parts.
Dans ces conditions le mélange se présente sous forme de particules de 0,5 à 10 mm et possède une densité en vrac de 0,25. Le temps t₂ observé en fonction du temps t₁ est indiqué au tableau III ci-après.
Claims (9)
- Decontamination article comprising a powdered polymer of bicyclo(2.2.1)hept-2-ene or the methyl derivative thereof, characterized in that it comprises at least one fine-mesh textile cover which is at least part-filled with the said polymer, this polymer being preagglomerated with an agent which imparts a certain level of plasticization to the polymer.
- Article according to Claim 1, characterized in that the said agent is chosen from liquid hydrocarbons and naphthenic, aromatic, paraffinic or petroleum oils, phthalates, adipates and sebacates, and alkylbenzenes.
- Article according to either of Claims 1 and 2, characterized in that the proportion of the said agent relative to the polymer is between 0.5 and 50% by weight.
- Article according to one of Claims 1 to 3, characterized in that the cover includes, preferably attached to at least one of its ends, at least one means of gripping which allows it to be pulled or towed by mechanical means.
- Article according to one of Claims 1 to 4, characterized in that the polymer contained in the cover has a particle size of between 0.5 and 20 mm.
- Article according to one of Claims 1 to 5, characterized in that the powdered polymer is mixed with at least one other absorbent agent.
- Process for absorbing a liquid pollutant product, characterized in that at least one fine-mesh textile cover which is at least part-filled with a powdered polymer of bicyclo(2.2.1)hept-2-ene, or the methyl derivative thereof, is placed on the surface of the said liquid, the said polymer being preagglomerated with an agent which imparts a certain level of plasticization to the polymer.
- Process according to Claim 7, characterized in that the liquid pollutant product is a petroleum product.
- Process according to Claim 8, characterized in that the number of covers is chosen such that the amount of powdered polymer contained in all of the covers is between 1/40 and 1 times the amount of pollutant product to be absorbed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8808855 | 1988-06-30 | ||
| FR8808855A FR2635332B1 (en) | 1988-06-30 | 1988-06-30 | ARTICLE AND METHOD FOR ABSORBING POLLUTANTS |
| CA000602047A CA1328652C (en) | 1988-06-30 | 1989-06-07 | Article and process for absorbing polluting products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0349363A1 EP0349363A1 (en) | 1990-01-03 |
| EP0349363B1 true EP0349363B1 (en) | 1996-05-29 |
Family
ID=25672791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89401625A Expired - Lifetime EP0349363B1 (en) | 1988-06-30 | 1989-06-12 | Article and process for absorbing polluting products |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5071564A (en) |
| EP (1) | EP0349363B1 (en) |
| JP (1) | JP2722406B2 (en) |
| CA (1) | CA1328652C (en) |
| DE (1) | DE68926550T2 (en) |
| ES (1) | ES2087088T3 (en) |
| FR (1) | FR2635332B1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360548A (en) * | 1989-02-14 | 1994-11-01 | Elf Atochem, S.A. | Process for absorbing organic polluting products |
| FR2643083B1 (en) * | 1989-02-14 | 1994-09-09 | Norsolor Sa | PROCESS FOR ABSORBING ORGANIC POLLUTANTS |
| FR2643381B1 (en) * | 1989-02-17 | 1994-06-10 | Norsolor Sa | COMPOSITION AND METHOD FOR ABSORBING POLLUTANT PRODUCTS |
| US5215407A (en) * | 1989-10-05 | 1993-06-01 | Brelsford Jeffrey A | Process of cleaning oil spills and the like |
| JP2621003B2 (en) * | 1992-04-27 | 1997-06-18 | ケイエフ・トレーディング株式会社 | Oil adsorption / coagulant |
| US5403491A (en) * | 1993-07-19 | 1995-04-04 | Holland; Herbert W. | Monitor well hydrocarbon absorber and solidifier |
| US5588785A (en) * | 1994-04-05 | 1996-12-31 | Holland; Herbert W. | Liquid hydrocarbon sorbing and solidifying pillow |
| AU2471695A (en) * | 1994-05-09 | 1995-11-29 | Herbert W. Holland | Method of removing organic compounds from air and water columns |
| GB2289688B (en) * | 1994-05-27 | 1998-11-11 | Fibertech Group Inc | Articles and methods for sorbing,filtering and disposing of fluid waste |
| US5518797A (en) * | 1994-06-24 | 1996-05-21 | Holland; Herbert W. | Marine vessel fuel spill prevention device |
| DE19521561A1 (en) * | 1995-06-19 | 1997-01-02 | Hoechst Ag | Absorbent |
| US5863440A (en) * | 1996-05-24 | 1999-01-26 | Abtech Industries, Inc. | Methods for ameliorating oil spills in marine and inland waters |
| US6541569B1 (en) | 1997-01-10 | 2003-04-01 | Abtech Industries, Inc. | Polymer alloys, morphology and materials for environmental remediation |
| CN1251782C (en) | 1997-01-10 | 2006-04-19 | 阿布特克工业公司 | Systems for ameliorating aqueous hydrocarbon spills |
| US6099723A (en) * | 1997-06-06 | 2000-08-08 | Abtech Industries, Inc. | Catchbasin systems for filtering hydrocarbon spills |
| US6106707A (en) * | 1998-02-18 | 2000-08-22 | Abtech Industries, Inc. | Curb-inlet storm drain systems for filtering trash and hydrocarbons |
| GB9811601D0 (en) * | 1998-05-30 | 1998-07-29 | Downing John D | Removing oil pollutant from water |
| US6080307A (en) * | 1998-09-29 | 2000-06-27 | Abtech Industries, Inc. | Storm drain systems for filtering trash and hydrocarbons |
| US6531059B1 (en) | 2000-10-05 | 2003-03-11 | Abtech Industries, Inc. | Suspended runoff water filter |
| JP4039045B2 (en) * | 2001-11-26 | 2008-01-30 | コニカミノルタホールディングス株式会社 | BANDPASS FILTER AND VIDEO DISPLAY DEVICE |
| WO2009142254A1 (en) | 2008-05-23 | 2009-11-26 | 石原産業株式会社 | Infra-red reflective material and production method thereof, and paint and resin composition containing the same |
| EP2949390B1 (en) * | 2014-05-28 | 2018-08-15 | Vera Margraf-Gerdau | Adsorption plant |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA707433B (en) * | 1969-11-03 | 1971-11-24 | Grace W R & Co | Method of removing oil from polluted water by means of specially packaged oil absorbing materials |
| US3607741A (en) * | 1970-02-19 | 1971-09-21 | Alfred Sohnius | Oil slick removal system |
| US3739913A (en) * | 1970-07-16 | 1973-06-19 | Johns Manville | Device for fencing and absorbing contaminating oil spills on water |
| FR2288709A1 (en) * | 1974-10-24 | 1976-05-21 | Charbonnages Ste Chimique | PROCESS FOR REMOVING PETROLEUM PRODUCTS FROM SOLID OR LIQUID SURFACES |
| CA1163570A (en) * | 1979-10-10 | 1984-03-13 | Alfred F. Crotti | Removal of oil from water |
| US4366067A (en) * | 1980-10-20 | 1982-12-28 | Golding Gordon R | Method and apparatus for removal and recovery of oil |
| FR2611146B1 (en) * | 1987-02-19 | 1991-02-15 | Charbonnages Ste Chimique | DEPOLLUTION ARTICLE AND METHOD FOR ABSORBING POLLUTANTS |
-
1988
- 1988-06-30 FR FR8808855A patent/FR2635332B1/en not_active Expired - Fee Related
-
1989
- 1989-06-07 CA CA000602047A patent/CA1328652C/en not_active Expired - Fee Related
- 1989-06-12 DE DE68926550T patent/DE68926550T2/en not_active Expired - Fee Related
- 1989-06-12 ES ES89401625T patent/ES2087088T3/en not_active Expired - Lifetime
- 1989-06-12 EP EP89401625A patent/EP0349363B1/en not_active Expired - Lifetime
- 1989-06-30 JP JP1169690A patent/JP2722406B2/en not_active Expired - Fee Related
-
1990
- 1990-10-01 US US07/593,267 patent/US5071564A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2635332B1 (en) | 1994-05-20 |
| DE68926550D1 (en) | 1996-07-04 |
| JPH0253887A (en) | 1990-02-22 |
| JP2722406B2 (en) | 1998-03-04 |
| FR2635332A1 (en) | 1990-02-16 |
| EP0349363A1 (en) | 1990-01-03 |
| US5071564A (en) | 1991-12-10 |
| DE68926550T2 (en) | 1996-11-28 |
| ES2087088T3 (en) | 1996-07-16 |
| CA1328652C (en) | 1994-04-19 |
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